US4939194A - Controllably and swiftly degradable polymer compositions and films and other products made therefrom - Google Patents

Controllably and swiftly degradable polymer compositions and films and other products made therefrom Download PDF

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Publication number
US4939194A
US4939194A US07/391,703 US39170389A US4939194A US 4939194 A US4939194 A US 4939194A US 39170389 A US39170389 A US 39170389A US 4939194 A US4939194 A US 4939194A
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complex
metal
polymer compositions
polymer
compositions according
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US07/391,703
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English (en)
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Gerald Scott
Dan Gilead
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Plastopil Hazorea
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Plastopil Hazorea
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0091—Complexes with metal-heteroatom-bonds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G13/00—Protecting plants
    • A01G13/02—Protective coverings for plants; Coverings for the ground; Devices for laying-out or removing coverings
    • A01G13/0256—Ground coverings
    • A01G13/0268—Mats or sheets, e.g. nets or fabrics
    • A01G13/0275—Films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0033—Additives activating the degradation of the macromolecular compound
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00—Soil-conditioning materials or soil-stabilising materials
    • C09K17/52—Mulches

Definitions

  • This invention relates to photogradable and thermally stable compositions based on homopolymers and copolymers of vinyl or vinylidene monomers such as polyethylene, polypropylene, polymethylpentene, polyvinlchloride, ethylene-propylene copolymers, condensation polymers, e.g. polyamides, polyesters, polyurethanes. etc., and intercopolymers containing unsaturation, as well as mixtures of such polymers, which degrade very rapidly on exposure to the environment owing to the presence of particular metal complexes. More particularly this invention relates to the controlled photogredation of vinyl polymers wherein the induction period, i.e. the duration between the exposure to sunlight (or the suitable radiation) and the beginning of said degradation is predetermined and may be very short.
  • the induction period i.e. the duration between the exposure to sunlight (or the suitable radiation) and the beginning of said degradation is predetermined and may be very short.
  • films of vinyl or vinylidene polymers and copolymers, especially ethylene polymers are widely used for many purposes including wraps and packaging materials and anyway for wrapping up different kind of products.
  • degradable polymer films is a desirable way of solving the problem of removal of mulching films as well as the problem of destroying plastic materials casually disposed after use.
  • the complex makes the composition stable in the manufacturing process in which it is brought to the molten state, usually extrusion or blow extrusion and during indoor use or in sufficiently sheltered places such as houses, shops, etc.
  • the metal complex splits with release of the metal in a photoactivated state which causes the rapid degradation of the polymer.
  • a film of degradable polymer containing metal complexes such as those claimed in the above mentioned patent, will pass upon being exposed to U.V.
  • embrittlement stage is characterized by an elongation at break substantially equal to zero.
  • the lasting time between the exposure to U.V. radiation and the attainment of the embrittlement point constitutes the so called "induction period”.
  • the induction period may widely vary according to different environmental conditions and/or the type of polymer composition but is rather unpredictable and cannot be controllably predetermined. This is the limit of the above mentioned invention.
  • thermoplastic polymer compositions in which the time to embrittlement can be predetermined and varied as one wishes with considerable precision especially in polyolefin films, said compositions containing carefully controlled amount of a metal complex of the type described in the above mentioned British specification (GB No. 1,356,107)in combination with an ultraviolet light stabilizing complex, preferably a nickel complex.
  • the single functions of the two types of complexes namely the complexes of iron (or Mn or Ce) on one hand and the complexes of nickel (or Co or Cu, or Zn) on the other, are very different from one another.
  • Iron complexes are powerful activators of U.V. degradion of a variety of polymers after a relatively short induction period whereas nickel-complexes are U.V. stabilizers.
  • compositions containing such a combination of the two aforementioned complexes are particularly useful for the production of films, especially mulching films which are allowed to remain on the soil for a certain and desired period of time and afterwards will degrade and will not interfere with the subsequent soil working operations such as ploughing or harvesting but actually will in fact be eliminated by those operations without the need of any change in them.
  • thermal stabilizing dithiolate complexes of a transition metal or of a metal of group II or IV of the periodic table of the elements notably zinc, nickel and cobalt dialkyl-dithiocarbamates.
  • the thermal stabilization attainable by metal complexes based on sulphur compounds and other metal complexes is well known and has been already shown in British Patent No. 1,586,344: some of those complexes (Ni, Cu, Co) are U.V. stabilizers (G.B. No. 1,356,107; 1,586,344).
  • thermal stabilizers such as those of the present invention, when used in combination with complexes of type (I) and in molar ratios ranging from 1:4 to 1:5, actually increase the rate of photodegradation reactions, thus giving significantly shorter embrittlement times than those attained with the oxygen complexes alone.
  • thermostabilising complexes with complexes of type (I) which are activators for the photodegradation of polymers, is the appearance of a very short but very well defined induction period upon exposure of degradable polymer compositions to sunlight.
  • the induction period which in the case of complexes of the type (I) used alone is normally absent, in the case of the present invention is very short but the stability of the compositions is absolute and complete during the induction period. Afterwards the degradation phase is sharp and rapid with total decay of the thermoplastic material.
  • thermostabilising complex for example Ni dithiocarbamate
  • photoactiving complex for example iron acetylacetonate
  • the most desirable ratios are lower than 0.3.
  • the molar ratio approaches 1 or is higher than 1, then the resulting observable effect is that of a noticable extension of induction period, with disappearance of the subsequent rapid and sharp decomposition.
  • the most characteristic aspects of the present invention are illustrated by means of the figures in the enclosed drawings wherein a comparison is made between the particular combination of the two types of complexes when used in the desirable ratios and the same combination but at different ratios as well as the iron dithiocarbamate referred to in Brit. Pat. No. 1,356,107.
  • the first figure refers to low density polyethylene (LDPE) films containing different amounts of iron dimethyldithiocarbamate (FeDMC), iron tris-acetylacetonate (FeAcAc) and zinc diethyldithiocarbamate (ZnDEC) and exposed in a weatherometer at the same time.
  • LDPE low density polyethylene
  • the abscissa (of FIG. 1 and 2) represents the exposure-time and the ordinate (of both figures) represents the variation of the carbonyl index (i.e. the ratio of the CO I.R. absorbance at a given time to the initial CO absorbance) as a measure of the polymer photodegradation.
  • Iron acetylacetonate promotes the immediate start of the degradative process while the second acts as a normal photoactivator (G.B. No. 1,356,107).
  • This invention consequently relates to polymer composition which are very quickly degradable under the action of ultra-violet light and/or sunlight wherein the induction period, namely, the delay time between the exposure to U.V. radiation and the start of said degradation is predetermined and may be very small.
  • the polymer compositions are characterized in that the photodegradation is promoted by means of the additional presence of at least one metal complex which is a powerful activator of said photo-degradation of polymers in combination with a very small amount of dithiolate metal complex which is a stabiliser for thermal degradation.
  • Molar ratios R of the activator complex to the thermal stabiliser are lower than 0.5 and preferably R ⁇ 0.3.
  • this invention relates to any protective or wrapping membrane and/or mulching film obtainable from said compositions by means of usual manufacturing processes such as extrusion or blow extrusion.
  • the thermoplastic vinyl polymer is preferably a film or fibre-forming polymer or copolymer such as polyethylene polypropylene, poly (4-methyl-1-pentene), or polystyrene or terpolymer which may contain unsaturation.
  • Other vinyl polymers such as polyvinylacetate, polyvinylchloride, polymethyl methacrylate, and polycrylonitrile and copolymers of the corresponding monomers, including vinylchloride-vinyl acetate copolymers, including graft copolymers with unsaturated polymers, as well as mixtures of such polymers, particularly with unsaturated polymers, can also be used in the compositions of the present invention.
  • This process can also be used for condensation polymers such as polyesters, polyamides and polyurethanes.
  • thermoplastic compositions of this invention may contain other compounding ingredients, such as blowing agents, various types of antioxidants, stabilisers, lubrificants, antistatic agents and antiblocking agents.
  • Antioxidants do not take part in the embrittlement process and therefore may be used in conventional amounts.
  • Inert pigments, dyes, other conventional Additives and carbon black may also be added to the polymer compositions.
  • pigments act as U.V. screening agents and increase the embrittlement time of the polymer and this is particularly true for carbon black as above already mentioned.
  • the photo-activating complex can be any organo-soluble transition metal complex in which the ligand is attached to the metal through oxygen.
  • Preferred complexing agents are ⁇ -di-ketones, ⁇ -ketoesters and among them acetylacetone.
  • transition metals are iron, cobalt and manganese.
  • the thermal stabilising complex is preferably a group II, group IV or a transition metal complex in which the complexing agent is any sulphur containing compound among the complexing agents disclosed in the earlier patents.
  • the complexing agent is any sulphur containing compound among the complexing agents disclosed in the earlier patents.
  • R, R 1 , R 2 , R 3 each represent hydrogen or an alkyl, aralkyl or amyl group, which may be unsubstituted or substituted as well as linked together to form heterocyclic rings.
  • Dithiocarbamates and the above mentioned derivatives thereof are the preferred complexing agents since they are substantially non toxic.
  • the preferred combinations of metal complexes in the thermoplastic polymer compositions according to the present invention are iron-acetylacetonate and Ni or Zn dialkyldithiocarbamates.
  • the concentration of the oxygen complexes is generally from 0,0005 to 0,5% by weight and preferably from 0,0005 to 0,2% by weight.
  • the concentration of the thermal stabilising sulphur containing metal complex depends on the desired relative molar ratio R of stabilising to activating complex.
  • the molar ratio R is generally lower than 0,5 preferably R ⁇ 0.3.
  • the relative concentrations to be used of the two metal complexes depend largely on the intended use of the finished article.
  • the following examples further illustrate the present invention.
  • Maximum processing temperatures were in the order 210° C.
  • the film thickness was 30 microns; however test carried out with greater thicknesses, up to the practical maximum of 100 microns, showed that the behaviour of the material was substantially the same for all thicknesses in the said range.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Soil Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Environmental Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Protection Of Plants (AREA)
US07/391,703 1986-02-27 1989-08-04 Controllably and swiftly degradable polymer compositions and films and other products made therefrom Expired - Fee Related US4939194A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8604849 1986-02-27
GB8604849A GB2187193B (en) 1986-02-27 1986-02-27 Controllably and swiftly degradable polymer compositions and films and other products made therefrom

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US07195445 Continuation 1988-05-16

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US (1) US4939194A (ja)
EP (1) EP0236005B1 (ja)
JP (2) JPH0662804B2 (ja)
AR (1) AR241193A1 (ja)
AT (1) ATE97149T1 (ja)
AU (1) AU602136B2 (ja)
BR (1) BR8700670A (ja)
CA (1) CA1295076C (ja)
DE (1) DE3788074T2 (ja)
DK (1) DK83987A (ja)
EG (1) EG19058A (ja)
ES (1) ES2007336A6 (ja)
FI (1) FI91417C (ja)
GB (1) GB2187193B (ja)
GR (1) GR870186B (ja)
IL (1) IL81069A (ja)
IT (1) IT1197825B (ja)
MA (1) MA20883A1 (ja)
MX (1) MX170812B (ja)
NO (1) NO168118C (ja)
PT (1) PT84372B (ja)
TN (1) TNSN87029A1 (ja)
ZA (1) ZA869758B (ja)

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5145779A (en) * 1991-05-03 1992-09-08 Iowa State University Research Foundation, Inc. Process of biodegradation of high molecular weight polyethylene by aerobic lignolytic microorganisms
US5274019A (en) * 1990-10-25 1993-12-28 Robinson Brothers Limited Photodegradable compositions
US5321065A (en) * 1990-01-23 1994-06-14 Pierre Bono Degradable plastics film including lignin as active vegetable filler
US5518730A (en) 1992-06-03 1996-05-21 Fuisz Technologies Ltd. Biodegradable controlled release flash flow melt-spun delivery system
US5639815A (en) * 1987-07-27 1997-06-17 Carnaudmetalbox Plc Packaging
US6653364B2 (en) * 2000-11-20 2003-11-25 Canon Kabushiki Kaisha Decomposable resin composition and method for producing the same
US20040062884A1 (en) * 2000-12-06 2004-04-01 Benzhong Hao Compositions for photodegradable and biodegradable plastic product and use thereof
US20040259974A1 (en) * 2003-06-18 2004-12-23 Gerald Scott Biodegradable polymer compositions with controlled lifetimes
US20070112107A1 (en) * 2003-09-22 2007-05-17 Takehiko Yamashita Flame-retardant resin composition, production method of the same and molding method of the same
US20090306452A1 (en) * 2008-05-19 2009-12-10 Payne Frederick C Apparatus for treating a contaminated media with a sorbent
US20100068283A1 (en) * 2008-09-16 2010-03-18 Searete Llc, A Limited Liability Corporation Of The State Of Delaware Ex VIVO modifiable particle or polymeric material medicament carrier
US20100068254A1 (en) * 2008-09-16 2010-03-18 Mahalaxmi Gita Bangera Modifying a medicament availability state of a final dosage form
US20100068152A1 (en) * 2008-09-16 2010-03-18 Searete Llc, A Limited Liability Corporation Of The State Of Delaware Ex vivo modifiable particle or polymeric based final dosage form
US20100069822A1 (en) * 2008-09-16 2010-03-18 Searete Llc, A Limited Liablity Corporation Of The State Of Delaware System for ex vivo modification of medicament release state
US20100068153A1 (en) * 2008-09-16 2010-03-18 Searete Llc, A Limited Liability Corporation Of The State Of Delaware Ex vivo activatable final dosage form
US20100069821A1 (en) * 2008-09-16 2010-03-18 Searete Llc, A Limited Liability Corporation Of The State Of Delaware Ex vivo modifiable medicament release-sites final dosage form
US20100068275A1 (en) * 2008-09-16 2010-03-18 Searete Llc, A Limited Liability Corporation Of The State Of Delaware Personalizable dosage form
US20100068233A1 (en) * 2008-09-16 2010-03-18 Searete Llc, A Limited Liability Corporation Of The State Of Delaware Modifiable dosage form
WO2012075337A2 (en) 2010-12-01 2012-06-07 Spinal Modulation, Inc. Directed delivery of agents to neural anatomy
WO2014110164A1 (en) * 2013-01-14 2014-07-17 Powergenix Systems, Inc. Pasted nickel hydroxide electrode and additives for rechargeable alkaline batteries
JP2015035964A (ja) * 2013-08-12 2015-02-23 みかど化工株式会社 農業用多層マルチフィルム
WO2019049112A1 (en) 2017-09-11 2019-03-14 Sorrento Therapeutics, Inc. RESINIFERATOXIN FORMULATION
WO2021202084A1 (en) 2020-03-30 2021-10-07 Sorrento Therapeutics, Inc. Treating pulmonary inflammatory disease associated with covid-19 by administering resiniferatoxin
WO2021257956A1 (en) 2020-06-19 2021-12-23 Sorrento Therapeutics, Inc. Administration of resiniferatoxin for treatment of bladder pain or bladder cancer
WO2022173916A1 (en) 2021-02-11 2022-08-18 Sorrento Therapeutics, Inc. Administration of resiniferatoxin for treatment of prostate cancer

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR960007311B1 (ko) * 1992-11-11 1996-05-30 대림산업주식회사 광분해성 폴리올레핀 필름 조성물
US20100229462A1 (en) * 2010-05-26 2010-09-16 Cerowa, Lp Degradable and Compostable Plastic Films for Agriculture

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB965054A (en) * 1961-12-28 1964-07-29 Hercules Powder Co Ltd Improvements in or relating to stabilization of polyolefins with nickel hydroxamates
GB1356107A (en) * 1970-07-22 1974-06-12 Scott G Polymer compositions
GB1400570A (en) * 1972-11-23 1975-07-16 Ici Ltd Prodegradant compositions comprising vinyl chloride polymers
GB1423655A (en) * 1972-05-18 1976-02-04 Ici Ltd Degradable polyvinyl chloride compositions
US4076689A (en) * 1976-05-14 1978-02-28 Phillips Petroleum Company Ultraviolet light stabilizer combination for polymers
GB1586344A (en) * 1977-09-21 1981-03-18 Gilead Dan Controllably degradable polymer compositions and films andother products made therefrom
US4519161A (en) * 1977-09-21 1985-05-28 Dan Gilead Agricultural process using controllably degradable polymer composition film

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3941759A (en) * 1972-03-01 1976-03-02 Owens-Illinois, Inc. Degradable plastics containing dual-function additive system
DE3670855D1 (de) * 1985-08-28 1990-06-07 Akzo Nv Photosensibilisierende zusammensetzungen und diese enthaltende unter lichteinwirkung abbaubare polymerzusammensetzung.

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB965054A (en) * 1961-12-28 1964-07-29 Hercules Powder Co Ltd Improvements in or relating to stabilization of polyolefins with nickel hydroxamates
GB1356107A (en) * 1970-07-22 1974-06-12 Scott G Polymer compositions
US4121025A (en) * 1970-07-22 1978-10-17 Gerald Scott Polymer compositions
GB1423655A (en) * 1972-05-18 1976-02-04 Ici Ltd Degradable polyvinyl chloride compositions
GB1400570A (en) * 1972-11-23 1975-07-16 Ici Ltd Prodegradant compositions comprising vinyl chloride polymers
US4076689A (en) * 1976-05-14 1978-02-28 Phillips Petroleum Company Ultraviolet light stabilizer combination for polymers
GB1586344A (en) * 1977-09-21 1981-03-18 Gilead Dan Controllably degradable polymer compositions and films andother products made therefrom
US4461853A (en) * 1977-09-21 1984-07-24 Dan Gilead Controllably degradable polymer compositions
US4519161A (en) * 1977-09-21 1985-05-28 Dan Gilead Agricultural process using controllably degradable polymer composition film

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Photo Initialized Oxidation of Polyethylene Effect of Photo Sensitizers, European Polymer Journal, vol. 10, pp. 1019 1028. *
Photo-Initialized Oxidation of Polyethylene Effect of Photo-Sensitizers, European Polymer Journal, vol. 10, pp. 1019-1028.

Cited By (41)

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US20040219320A1 (en) * 1987-07-27 2004-11-04 Constar International, Inc. Packaging
US5639815A (en) * 1987-07-27 1997-06-17 Carnaudmetalbox Plc Packaging
US5955527A (en) * 1987-07-27 1999-09-21 Carnaudmetalbox Plc Packaging
US20050179002A1 (en) * 1987-07-27 2005-08-18 Constar International, Inc. Packaging
US5321065A (en) * 1990-01-23 1994-06-14 Pierre Bono Degradable plastics film including lignin as active vegetable filler
US5274019A (en) * 1990-10-25 1993-12-28 Robinson Brothers Limited Photodegradable compositions
US5145779A (en) * 1991-05-03 1992-09-08 Iowa State University Research Foundation, Inc. Process of biodegradation of high molecular weight polyethylene by aerobic lignolytic microorganisms
US5518730A (en) 1992-06-03 1996-05-21 Fuisz Technologies Ltd. Biodegradable controlled release flash flow melt-spun delivery system
US20040010051A1 (en) * 2000-11-20 2004-01-15 Canon Kabushiki Kaisha Decomposable resin composition and method for producing the same
US6653364B2 (en) * 2000-11-20 2003-11-25 Canon Kabushiki Kaisha Decomposable resin composition and method for producing the same
US7019043B2 (en) 2000-11-20 2006-03-28 Canon Kabushiki Kaisha Decomposable resin composition and method for producing the same
US20040062884A1 (en) * 2000-12-06 2004-04-01 Benzhong Hao Compositions for photodegradable and biodegradable plastic product and use thereof
US7291664B2 (en) * 2000-12-06 2007-11-06 Changtai Han Multicomponent composition for photodegradable and biodegradable plastic articles and the use thereof
US20040259974A1 (en) * 2003-06-18 2004-12-23 Gerald Scott Biodegradable polymer compositions with controlled lifetimes
US20060160922A1 (en) * 2003-06-18 2006-07-20 Gerald Scott Biodegradable polymer compositions with controlled lifetimes
US7750069B2 (en) 2003-09-22 2010-07-06 Panasonic Corporation Flame-retardant resin composition, production method of the same and molding method of the same
US20070112107A1 (en) * 2003-09-22 2007-05-17 Takehiko Yamashita Flame-retardant resin composition, production method of the same and molding method of the same
US20090306452A1 (en) * 2008-05-19 2009-12-10 Payne Frederick C Apparatus for treating a contaminated media with a sorbent
US20100068235A1 (en) * 2008-09-16 2010-03-18 Searete LLC, a limited liability corporation of Deleware Individualizable dosage form
US20100068283A1 (en) * 2008-09-16 2010-03-18 Searete Llc, A Limited Liability Corporation Of The State Of Delaware Ex VIVO modifiable particle or polymeric material medicament carrier
US20100068278A1 (en) * 2008-09-16 2010-03-18 Searete Llc, A Limited Liablity Corporation Of The State Of Delaware Ex vivo modifiable medicament release-associations
US20100069822A1 (en) * 2008-09-16 2010-03-18 Searete Llc, A Limited Liablity Corporation Of The State Of Delaware System for ex vivo modification of medicament release state
US20100068266A1 (en) * 2008-09-16 2010-03-18 Searete Llc, A Limited Liability Corporation Of The State Of Delaware Ex vivo-modifiable multiple-release state final dosage form
US20100068153A1 (en) * 2008-09-16 2010-03-18 Searete Llc, A Limited Liability Corporation Of The State Of Delaware Ex vivo activatable final dosage form
US20100069821A1 (en) * 2008-09-16 2010-03-18 Searete Llc, A Limited Liability Corporation Of The State Of Delaware Ex vivo modifiable medicament release-sites final dosage form
US20100068256A1 (en) * 2008-09-16 2010-03-18 Searete Llc, A Limited Liability Corporation Of The State Of Delaware Ex vivo modifiable medicament release-substance
US20100068277A1 (en) * 2008-09-16 2010-03-18 Searete Llc, A Limited Liability Corporation Of The State Of Delaware Ex vivo modifiable multiple medicament final dosage form
US20100068254A1 (en) * 2008-09-16 2010-03-18 Mahalaxmi Gita Bangera Modifying a medicament availability state of a final dosage form
US20100068152A1 (en) * 2008-09-16 2010-03-18 Searete Llc, A Limited Liability Corporation Of The State Of Delaware Ex vivo modifiable particle or polymeric based final dosage form
US20100068233A1 (en) * 2008-09-16 2010-03-18 Searete Llc, A Limited Liability Corporation Of The State Of Delaware Modifiable dosage form
US20100068275A1 (en) * 2008-09-16 2010-03-18 Searete Llc, A Limited Liability Corporation Of The State Of Delaware Personalizable dosage form
US8753677B2 (en) 2008-09-16 2014-06-17 The Invention Science Fund I, Llc Ex vivo modifiable multiple medicament final dosage form
WO2012075337A2 (en) 2010-12-01 2012-06-07 Spinal Modulation, Inc. Directed delivery of agents to neural anatomy
WO2014110164A1 (en) * 2013-01-14 2014-07-17 Powergenix Systems, Inc. Pasted nickel hydroxide electrode and additives for rechargeable alkaline batteries
US9337483B2 (en) 2013-01-14 2016-05-10 Powergenix Systems, Inc. Pasted nickel hydroxide electrode and additives for rechargeable alkaline batteries
CN104995782A (zh) * 2013-01-14 2015-10-21 鲍尔热尼系统公司 用于可再充电碱性蓄电池的膏状氢氧化镍电极和添加剂
JP2015035964A (ja) * 2013-08-12 2015-02-23 みかど化工株式会社 農業用多層マルチフィルム
WO2019049112A1 (en) 2017-09-11 2019-03-14 Sorrento Therapeutics, Inc. RESINIFERATOXIN FORMULATION
WO2021202084A1 (en) 2020-03-30 2021-10-07 Sorrento Therapeutics, Inc. Treating pulmonary inflammatory disease associated with covid-19 by administering resiniferatoxin
WO2021257956A1 (en) 2020-06-19 2021-12-23 Sorrento Therapeutics, Inc. Administration of resiniferatoxin for treatment of bladder pain or bladder cancer
WO2022173916A1 (en) 2021-02-11 2022-08-18 Sorrento Therapeutics, Inc. Administration of resiniferatoxin for treatment of prostate cancer

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IT8621782A0 (it) 1986-09-22
IT1197825B (it) 1988-12-06
JPH0813227B2 (ja) 1996-02-14
IT8621782A1 (it) 1988-03-22
IL81069A0 (en) 1987-03-31
NO870801L (no) 1987-08-28
EP0236005A3 (en) 1989-01-25
GR870186B (en) 1987-06-05
FI870616A (fi) 1987-08-28
EG19058A (en) 1994-09-29
PT84372B (pt) 1989-10-04
AR241193A1 (es) 1992-01-31
NO168118B (no) 1991-10-07
JPH07143827A (ja) 1995-06-06
MA20883A1 (fr) 1987-10-01
FI91417C (fi) 1994-06-27
FI91417B (fi) 1994-03-15
ES2007336A6 (es) 1989-06-16
TNSN87029A1 (fr) 1990-01-01
NO870801D0 (no) 1987-02-26
GB2187193B (en) 1989-11-08
BR8700670A (pt) 1987-12-15
EP0236005A2 (en) 1987-09-09
NO168118C (no) 1992-01-15
GB8604849D0 (en) 1986-04-03
AU602136B2 (en) 1990-10-04
IL81069A (en) 1990-07-12
DK83987A (da) 1987-08-28
MX170812B (es) 1993-09-20
FI870616A0 (fi) 1987-02-13
DE3788074T2 (de) 1994-03-03
DK83987D0 (da) 1987-02-19
EP0236005B1 (en) 1993-11-10
CA1295076C (en) 1992-01-28
JPH0662804B2 (ja) 1994-08-17
JPS62199653A (ja) 1987-09-03
GB2187193A (en) 1987-09-03
ZA869758B (en) 1987-09-30
DE3788074D1 (de) 1993-12-16
ATE97149T1 (de) 1993-11-15
PT84372A (en) 1987-03-01
AU6913387A (en) 1987-09-03

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